Multi-layer color photographic silver halide light-sensitive materials

ABSTRACT

A multi-layer type color photographic light-sensitive material characterized in that a merocyanine dye having the following general formula I wherein X is selected from the group consisting of a sulfur atom, a selenium atom, an oxygen atom, and WHEREIN EACH OF R1, R2 and R3 is selected from the group consisting of a hydrogen atom, an alkyl group, a substituted alkyl group, an aryl group, and a substituted aryl group; and wherein Z represents an atomic group necessary to complete a heterocyclic ring, which may be substituted, is incorporated in at least one layer of the multi-layer type color photographic light-sensitive material, said multi-layer type color photographic light-sensitive material having on a support at least two silver halide photographic emulsion layers is disclosed.

United States Patent [191 Hayashi et al.

[ 1 Jan. 30, 1973 [75] Inventors: Jun Hayashi; Akira Sato, Kanagawa,

Japan [73] Assignee: 'Fuji Photo Film Co., Ltd., Minami,

'1 Ashigara-shLKanagawa,Japan [22] Filed: Sept. 8, 1970 [21] Appl. No.: 70,554

[30] Foreign Application Priority Data Sept. 5, 1969 Japan ..44/7068l [52] U.S. Cl ...96/74, 96/139 [51] Int. Cl ..G03c 1/76, 003C 3/00 [58] Field of Search ..96/139, 74

[56] References Cited UNITED STATES'PATENTS 2,504,615 4/1950 Anish .....96/l39 2,692,829 10/ l 954 Aubert ct al. ..96/1 39 2,944,901 7/ l 960 Carroll ....96/ l 39 3,384,486 5/1968 Taber etal. ..96/74 3,480,434 11/1969 Hanna t ..96/74 3,573,916 4/1971 Yost et al. ..96/74 Primary Examiner-J. Travis Brown Attorney-Sughrue, Rothwell, Mion, Zinn and Macpeak 57 i ABSTRACT A multi-layer type color photographic light-sensitive material characterized in that a merocyanine dye having the following general formula 1 wherein X is selected from the group consisting of a sulfur atom, a selenium atom, an oxygen atom, and

wherein each of R,, R and R is selected from the group consisting of a hydrogen atom, an alkyl group a substituted alkyl group, an aryl group, and a substituted aryl group; and wherein Z represents an atomic group necessary to complete a heterocyclic ring, which may be substituted, is incorporated in at least one layer of the muIti-layer type color photographic light-sensitive material, said multi-layer type color photographic light-sensitive material having on a support at least two silver halide photographic emulsion layers is disclosed.

10 Claims, No Drawings MULTI-LAYER COLOR PI-IOTOGRAPI-IIC SILVER HALIDE LIGHT-SENSITIVE MATERIALS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multi-layer color photographic light-sensitive material showing improved color contrast due to the interimage effect.

2. Description of the Prior Art In a multi-layer color photographic light-sensitive material having on a support a red-sensitive emulsion layer, a green-sensitive emulsion layer and a blue-sensitive emulsion layer, the dye formed by the reaction of the oxidation product of an aromatic primary amino color developing agent and a color former or a coupler has the property of absorbing to some extent light other than that to be absorbed. For instance, a magenta dye absorbs blue light and red light to some extent'in addition to the green light to be absorbed. Similarly, a yellow dye and cyan dye absorb to some extent light other than blue light and red light respectively. This undesirable and unnecessary absorption by the dye tends to creasing this interimage effect is not well known. For 1 instance, although it is known that this interimage effect is caused by using a coupler capable of releasing a development inhibiting material on coupling, such as a benztriazole or a mercapto compound or a compound reduce the color contrast and hence tends to darken I the color obtained and to reduce the saturation.

The reduction of the saturation of color by this unnecessary absorption of the dye may be improved-to some extent by the inter-image effect. The interimage effect is a phenomenon wherein the formation of a dye image in one photographic emulsion layer influences the formation of the dye image in other photographic emulsion layers in a multi-layer color photographic light-sensitive material. With the interimage effect the color contrast can be increased.

The interimage effect increasing the color contrast can be explained as follows. A silver halide emulsion sensitive to red light and designed to give an image of a cyan dye after development is applied to a film base and then a silver halide emulsion sensitive to blue light and designed to give an image of a yellow dye after development is further applied to the red-sensitive emulsion layer. The sample thus obtained is cut into two parts. One (Sample I) of the parts is wedge exposed to red light only, while the other part (Sample II) is exposed to red light at the same exposure amount and then to blue light giving the same photographic effect as above. Thereby a wedge image is formed in only the lower red-sensitive emulsion layer of Sample I and also a wedge image is formed in the upper blue-sensitive layer and the lower red-sensitive layer of Sample ll. After development the contrasts of the cyan dye images formed in the red-sensitive layers of Sample land Sample II are evaluated by measuring their densities. When the contrast of the cyan dye image of Sample I is higher than the contrast of the cyan dye image of Sample I],

the interimage effect has occurred. In a multi-layer color photographic light-sensitive material having a red-sensitive layer, a green-sensitive layer and a blue- 7 C.A. Horton in Journal of the Optical Society of Amersuch as hydroquinone capable of releasing an inhibiting material on development, such as iodine ions or a mercapto compound, such compounds are generally unstable, are readily decomposed or cause great desensitization, which limits their selection. Accordingly, it has hitherto been considered difficult to increase the contrast by the interimage effect without adversely influencing the photographic properties.

An object of. this invention is to provide a color photographic image in which the unnecessary absorption of the dye is corrected by the interimage efiect.

Another object of this invention is to provide a color photographic image having a high color saturation unaccompanied with any reduction in sensitivity.

SUMMARY OF THE INVENTION As a result of the inventors investigations, the inventors have found that the interimage effect occurs markedly by incorporating a merocyanine dye in at least one photographic emulsion layer of a multi-layercolor photographic light-sensitive material havingat least two silver halide photographic emulsion layers.

The merocyanine dye used in this invention has the general formula [I] wherein X represents a sulfuratom, aselenium atom, an oxygen atom or wherein R R and R each represents a hydrogen atom, an unsubstituted alkyl radical or an unsubstituted or substituted aryl radical; and whereinZ represents the atomic groupnecessary for forming a heterocyclic ring, which may be substituted.

DETAILED DESCRIPTION OF THE INVENTION The merocyanine dye represented by the above formula will be explained now in greater detail.

In general, in formula [I], X is a sulfur atom, a selenium atom, an oxygen atom, or

and each of R R and R is a hydrogen atom; an alkyl Compound group, such as a methyl group, an ethyl group, an npropyl group, an n-butyl group, an iso-butyl group, an ass n-amyl group, and the like; a substituted alkyl group 5 I such as a Z-methoxyethyl group, a 2-hydroxyethyl group, an allyl group (or a vinylmethyl group), a benzyl group, a phenethyl group, a carboxymethyl group, a i o carboxyethyl group, a sulfomethyl group, a sulfopropyl group, a sulfobutyl group, a 4-carboxyphenethyl group,- 0 a 4-sulfophenethyl group, and the like; an aryl group such as a phenyl group; or a substituted aryl group such OUND as a 4-carboxyphenyl group, a 4-sulfophenyl group, and

the like. 7 I Also, Z is an atomic group necessary to complete a heterocyclic ring. Suitable such heterocyclic rings are thiazolines such as 4-methylthiazoline, 4-phenylthiazoline, and the like; thiazoles such as thiazole, 4- 0:0 methylthiazole, 4-phenylthiazole, S-methylthiazole, I 4,5-dimethylthiazole, and the like; benzthiazoles such as benzthiazole, 4-chlorobenzthiazole, 5- (arm I g 32115 chlorobenzthiazole, 6-chlorobenzthiazole, 7- COMPOUND 4 chlorobenzthiazole, S-methylbenzthiazole, 6- 0 S bromobenzthiazole, S-phenylbenzthiazole, S-methoxybenzthiazole, 6-methoxybenzthiazole', 5- I \C=C/ \C=S iodobenzthiazole, S-ethoxybenzthiazole, -hydrox- I ybenzthiazole, 5-carboxyethylbenzthiazole, 6-sulv f fobenzthiazole, andthe like; naphthothiazoles, such as 02115 0 naphtho[l,2]c[2,1]-thiazole, 5- methoxynaphtho[2,l]-thiazole, 7 7-sulfoethyl- I naphtho[l,2]-thiazole, and the like; oxazoles, such as 4-methyloxazole, S-methyloxazole, 4-phenyloxazole, 4- COMPOUND 5 ethyloxazole, 4,5-dimethyloxazole, and the like; CHZCOOH benzoxazoles, such as benzoxazole, S-chlo'robenzox- S N 'azole, S-methylbenzoxazole, S-phenylbenzoxazole, 5,6- dimethylbenzoxazole, 5-methoxybenzoxazole, 5- 0:0 C25 hydroxybenzoxazole', 6-sulfobenzoxazole, 6-carbox- L yethylbenzoxazole, and the like; naphthoxazoles, such u as naphtho [l,2]oxazole, naphtho[2,l] oxazole, and O the like; selenazoles, such as 4methylselenazole, 4- 40 COMPOUND 6 phenylselenazole, and the like; benzselenazoles, such s as benzselenazole, 5-chlorobenzselenazole, S-methox I ybenzselenazole, S-hydroxybenzselenazole, tetrahydrobenzselenazole, and the like; H naphthoselenazoles, such as naphtho[l,2] selenazole, 6 0 CHECOOH naphtho[2,l ]cselenazole, and the like; indolenines such as 3,3-dimethylindolenine, 3,3-diethylindolenine, COMPOUND 3,3,7-trimethylindolenine, and the like; 8 benzimidazoles, such as 3-ethylbenzimidazole, 3-phenc= \=s ylbenzimidazole, 5-chlorobenzimidazole, 1,3-diethyl- 5,6-dichlorobenzimidazole, and the like; I N H 8 naphthoimidazoles, such as 3-ethylnaphtho[2,l 2 5 ]imidazole, 3-phenylnaphtho[1,2]imidazole, and the CaHsSOrHNUJzHOs like; 2-quinolines, such as quinoline, 3-methylquin- COMPOUND 8 oline, S-methylquinoline, 7-methylquinoline, 8- s methylquinoline,- 6-chloroquinoline, fi-methoxyquinoline, -hydroxyquinoline, and the like; and 2- pyridines, such as pyridine, S-methylpyridine, and the N like. lag-280g 0 $2115 The merocyanine dyes used in this invention are illustrated by the following examples given below but Q they are not to be limited thereby. Compound (1) ""cg g gflgg'f EES 9 S\ /S\ CIJQH5 c=s 01 N I /c=c I v I c=o =s CH} C-N 01 N N COMPOUND COMPOUND 11 S COMPOUND 13 s 6 ooMPoU ND 14 CzHs wherein R and Z have the same meanings as described above in regard to the general formula [1]; R

represents an alkyl group or an aryl group and X" [III] wherein X and R have the same meanings as described above in regard to the general formula [I] in the presence of an organic base, such as triethylamine, in an alcoholic solvent.

For instance, the merocyanine dyes used in this invention can be readily synthesized by referring to the description in FM. Famer, The Cyanine Dyes and Related Compounds, p. 511; John Wiley & Sons Co., as well as in the specifications of US. Pat. Nos. 2,493,748 and 2,519,001.

The merocyanine dye of this invention can be incorporated in a multi-layer color photographic light-sensitive material by incorporating the dye in at least one of layers consisting of the silver halide emulsion layers of the color photographic light-sensitive material and the layers adjacent to the silver halide emulsion layers, such as a yellow filter layer, an antihalation layer, an intermediate layer, or a protective layer.

I The amount of the merocyanine dye usediri this in- 7' vention depends upon the nature of the multi-layer color photographic light-sensitive material and the manner used in developing the material but where the merocyanine dye is incorporated in a silver halide emulsion layer of multilayer color photographic light- 1 sensitive material, the amount of the dye is suitably from 6 to 600 mg per mol of silver halide and where the merocyanine dye is incorporated in an emulsion layer adjacent to the silver halide emulsion layer, the amount of the dye is suitably from 6 to 600 mg per 100 g of gelatin. However, it is to be understood that variance from these amounts can be made where desired. As the solvent for the merocyanine dye suitable solvents are those which do not adversely influence silver halide photographic emulsions, such as water, methanol, and

' For obtaining the interimage effect in this invention the multilayer color photographic light-sensitive material is processed at an ordinary temperature, i.e., from 20 to 30C, but the material may be processed at a higher temperature, i.e., at from 30 to C or temperatures higher than that if desired.

The marazyahinaa' e fihisihveiiiiofilri bamized in any of the processed providing color photographic images, i.e., in any of the processes of forming dye images corresponding to the proportion of silver reduced from silver halide by developing a multi-layer color photographic light-sensitive material having at least two photographic emulsion layers, each containing a silver halide dispersion in a hydrophilic colloidal mediumJFor instance, the merocyanine dye of this invention is effectively used in a reversal color photo-' graphic process, i.e., a process for obtaining a positive color image by exposing a multi-layer color photographic light-sensitive material having at least two silver halide photographic emulsion layers, each having a sensitivity in a different wavelength region, developing the light-sensitive material in a black and white developer solution to form a negative silver image and thereafter developing the silverhalide emulsion particles at the areas which have not been developed by the black and white developing solution to form a positive color image.

. Reversal color photography is classified into two systems, Le, a coupler-in-developer type color photographic system, and a coupler-in emulsion layer color photographic system. In the former the dye images are obtained by developing successively an exposed color photographic light-sensitive material in color developer solutions, each of the solutions containing a diffusible coupler to be coupled in each of the different color layers. in the latter each layer contains a'diffusion resisting coupler to be coupled in each of the different color layers incorporated in a multi-layer type color photographic light-sensitive material with" the dye images being obtained by processing the light-sensitive material in a color developer solution containing no couplers.

The merocyanine dye of this invention can be ap plied with good results to both types of the reversal color photographic systems.

The merocyanine dye of the'present invention also can be used in a system in which a multi-layer type color photographic light-sensitive material, having at least two layers of a silver halide photographic emulsion, each containing a diffusion resisting coupler and each sensitized to a different wave length region, is exposed and then immediately color-developed to provide a negative colorimage.

Furthermore, the merocyanine dye of this invention can be used in a color photographic diffusion transfer process, in which the diffusion of a developing solution,

couplers, and dyes in conformity with the image from the light-sensitive layer to a reception layer when the light-sensitive layer is contacted closely with the reception layer during development,as described in the specifications of US. Pat. Nos. 2,559,643, 2,698,798; and 3,227,551.

Still further, the merocyanine dye of this invention can be used in a silver dye bleaching color photography in which a dye image is obtained by bleaching the dye at the areas where the silver is present, as disclosed in the specifications of US. Pat. Nos. 2,020,775 and 2,410,025.

In the multi-layer type color photographic light-sensitive material of this invention, it is desirable to apply a red-sensitive silver halide photographic emulsion, a,

green-sensitive silver halide emulsion, and a blue-sensitive silver halide emulsion to a support in this order.

Also, in the multi-layer type color photographic light-sensitive material of this invention, it is desirable to form the cyan, magenta and yellow images in the red-sensitive, green-sensitive, and blue-sensitive silver halide emulsion layers, respectively, after development..

l-lowever, systems other than those stated above can be employed in this invention.

The silver halide emulsion used in the present invention can be photographic emulsions containing silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, or silver chloroiodobromide. in particular, when a photographic emulsion layer containssilver chloroiodide, silver iodobromide or silver chloro-iodobromide'"having an iodine content of from 1 to mol percent, better results can be obtained.

' compound suchas a gold (I) complex salt of thiocyanate; a polyalkyleneoxide derivative, or a combination thereof. Furthermore, the silver halide photographic emulsion used in this invention can be spectrally sensitized using a cyanine dye such as 1,1- diethylcyanine iodide, l,l -diethyl-9-methylcarbocyanine bromide, anhydro-S,5-diphenyl-9-ethyl-3,3- di(2sulfoethyl)-benzoxazolocarbocyanine hydroxide, and the like, ora combination thereof. Still further, the silver halide photographic emulsion used in this invention can contain a developing agent capable of releasing a development inhibitor such as 2-iodo-5-pentadecylhydroquinone, 2-methyl-5-( l-phenyl-5- tetrazolylthio)-hydroquinone, and the like; a stabilizer such as 4-hydroxy-6-methyl-l ,3,3a-7-tetraazaindene, benzirnidazole, 1-phenyl-5-mercaptotetrazole, and the like; a hardening agent such as formaldehyde, mucobromic acid, and the like, and a wetting agent such as saponine; sodium alkylbenzenesulfonate, and the like.

The invention will now be explained in greater detail by reference to the following examples. in the following examples,"two types of color photographic systems were employed. That is to.say, the so-called coupler-indeveloper color photographic system in which couplers are supplied from color developer solutions and the socalled coupler-in-emulsion layer type color photographic system in which couplers are incorporated in the photographic emulsion layers of color photographic light-sensitive materials, were employed.

in the examples of the present invention shown below, a multilayer type color photographic light-sensitive material having the following compositions was employed in the coupler-in-developer type color photographic system.

COUPLER-lN-DEVELOPER TYPE COLOR PHOTOGRAPHIC SYSTEM silver content waslS mg/l 00 cm.

Third Layer The yellow filter layer; a layer formed by coating a yellow 'colloidal silver dispersion, prepared by dispersing colloidal silverin gelatin so that the silver content was 2.5 ing/ cm.

Fourth Layer i The blue-sensitive gelatino silver halide emulsion layer; a layer formed by coating a high speed silver iodobromide emulsion containing no coupler so that the silver content was 20 mg/ 100 cm.

1 2 3 Water Washing 1n the examples shown below relating to the couplerin-developer type color photographic system, the multi-layer type color photographic light-sensitive materials were subjected to the following developing procedures:

Process Time (min) Hardening W t r W sh ng Negative Development The temperature of the processing baths used above was 27C. The compositions of the baths were as follows:

Hardening Bath Sodium Hexametaphosphate 2.0 g Sodium Bisulfite 5.0 g Sodium Pyrophosphate (10 H,0) 15.0 g Sodium Sulfate 100.0 g Potassium Bromide 2.0 g Sodium Hydroxide 0.1 g 37% Formaldehyde 17.0 cc Water added to make the total volume to 1000 cc. Negative Developer Solution N-Methyl'p-aminophenol Sulfate 5.0 g Sodium Sulfite 79.0 g Hydroquinone 2.0 g Sodium Hydroxide 1.0 g Sodium Carbonate (1 11,0) 41.0 0.1% Potassium Iodide lZS cc 3 Potassium Bromide V H A w 3.6 g Sodium Hydroquinone Monosulfonate 4.0 g Potassium Thiocyanate 2.0 g 0.5% 6-Nitrobenzoindazole Nitrate 5.0 cc Water added to make the total volume to 1000 cc. Cyan Color Developer Solution Potassium Bromide 2.9 g 1% 6-Nitrobenzoimidazole Nitrate 3.0 cc I 0.1% Potassium lodide 1 1.0 cc Sodium Sulflte 10.0 g Sodium Sulfate 60.0 g Potassium Thiocyanate 1.2 g 4-Amino-3-methyl-N-eth l-N-(flhydroxyethyl)-aniline Su fate 2.5 g Sodium Hydroxide 3.4 g l-Hydroxy-N-(2-propionamidophenethyl)- 2-na hthamide 1.5 g 2,4- ichloro-l-naphthol 0.2 g 2-Methyl-2,4-pentandiol 10.0 cc Polyoxyethylene-methylphen lEther 0.5 g Monobenzyl-p-aminophenol ydro- I chloride 0.4 g P-Aminophenol Hydrochloride 0.12 g Water added to make the total volume to 1000 cc. Yellow Color Developer Solution Sodium Sulfite 10.0 g Potassium Bromide 0.65 g 0.1% Potassium Iodide 29.0 cc l-%6-Nitrobenzoimidazole 10.0 cc Sodium Sulfate 64.0 g N,N-Diethyl-p-phenylenediamine Hydrochloride 3.0 g Sodium H droxide 2.4 g Z-Methyl- ,4-pentandiol 20.0 cc Z-Benzoyl-2'-methoxyacetanilide 1.8 g Diethylhydroxylamine 0.3 cc 1 Polyoxyethylene-methylphenyl Ether 0.8

Water'added to make the total volume to 1000 cc. Magenta Color Developer Solution Concentrated Sulfuric Acid 2.0 cc Trisodium Phosphate (12 H,0) 40.0 g Sodium Sulfite 5.0 g Potassium Thiocyanate 1.2 g 0.1% Potassium Iodide 7.5 cc Potassium Bromide 0.6 g 4-Amino-3-methyl-N-(fl-methylsulfonamidoethyl) aniline Sulfate 2.0 g

Ethylenediamine 6.0 cc Sodium Hydroxide 0.3 g l-(2,4,6-Trichlorophenyl) 3-(4- nitroanilino)-5-pyrazolone 1.7 g 2-Methyl-2,4-pentandiol 10.0 cc Sodium Sulfate 50.0 g Polyoxyethylene-methylphenyl Ether 0.5 g

Water added to make the total volume to 1000 cc. Bleaching Solution Potassium Ferricyanide 100.0 g

Potassium Bromide 30.0 g

Water added to make the total volume to 1000 cc. Fixing Solution 1 Sodium Thiosuliate Sodium Sulfite Water added to make the total volume to 1000 cc.

In the examples shown below relating to the so-called coupler-in-emulsion layer type color photographic system, a multi-layer type color photographic light-sensitive material having the following composition was used.

COUPLER-lN-EMULSION LAYER COLOR PHOTOGRAPHIC SYSTEM On a cellulose triacetate film were coated the following different kinds of layers in the following order: First Layer: (Lowermost Layer) The antihalation layer; a layer formed by coating a gray colloidal silver dispersion prepared by dispersing colloidal silver in gelatin so that the silver content was 3 mg/ cm Second Layer An intermediate layer; a layer formed by coating a gelatin solution so that the content of the gelatin was 3.4 mg/l00 cm Third Layer The red-sensitive silver halide emulsion layer; a layer formed by coating a high speed gelatino silver iodobromide emulsion having red sensitivity due to a sensitizing dye and containing a cyan coupler (a coupler emulsion prepared by dispersing in gelatin a solution of 1- hydroxy-4-chloro-N-dodecyl-2-naphthamide in -tricresyl phosphate) so that the silver content was 10 mg/ 100 cm. Fourth Layer An intermediate layer; a layer formed by coating a gelatin solution so that the gelatin content was 13.4 mg/lOO-cm. Fifth Layer The green-sensitive gelatino silver halide emulsion layer; a layer formed by coating a high speed silver bromide emulsion having green sensitivity due to sensitizing dye and containing a magenta coupler (a coupler emulsion prepared by dispersing in gelatin a solution of l-(2,6-dichloro-4-methoxyphenyl)-3-[3- a-(2. 4-ditert-amylphenoxy )propionamido benzamido -5 pyrazolone in dibutylphthalate) so that the silver content was 15 mg/l00 cm Sixth Layer The yellow filter layer; a layer, prepared by coating a yellow colloidal silver dispersion formed by dispersing colloidal silver in gelatin so that the silver content was 2.5 mg/100cm Seventh Layer The blue-sensitive silver halide emulsion layer; a layer formed by coating a high speed gelatino silver iodobromide emulsion containing a yellow coupler (a coupler emulsion prepared by dispersing in gelatin a solution of 2-benzoyl-2-chloro-,5'-tridecanoyloxyacetanilide in dibutylphthalate) so that the silver content was 15 mg/lOO cm.

Process Time (min.) Hardening Water Washing First Development Water Washing Reversal Exposure Second Development Water Washing Bleaching Water Washing Fixing Water Washing The temperature of the above processing baths was 30C The compositions of the baths used were as follows:

Hardening Bath Sulfuric Acid (lzl) 5.4 cc Sodium Sulfate 150.0 g Sodium Acetate 20.0 g 30% Pyruvaldehyde 40.0 cc 37% Formaldehyde 20.0 cc Water added to make the total volume to 1000 cc.

First Developer Solution N-Methyl-p-aminophenol Sulfate 2.0 g Sodium Sulfite 90.0 g Hydroquinone 8.0 g Sodium Carbonate (l H,0) 52.5 g Potassium Bromide 5.0 g Potassium Thiocyanate 1.0 g Water added to make the total volume to i000 cc.

Second Developer Solution Benzyl Alcohol 5.0 cc Sodium Sulfite 5.0 g Hydroxylamine Hydrochloride 2.0 g 3-Methyl-4-arnino-N-ethyl'N-(B- methylsulfonamidoethyl)aniline Sulfate L5 g Potassium Bromide l.0 g Trisodium Phosphate 30 g Sodium Hydroxide 0.5 g Ethylenediamine (70% aqueous solution) 7 cc Water added to make'the total volume to i000 cc.

Bleaching Solution Ferricyanide 100 g Sodium Acetate 40 g Glacial Acetic Acid 20 g Potassium Bromide 30 g Water added to make the total volume to i000 cc.

Fixing Solution Sodium Thiosulfate 150 g Sodium Acetate 70 g Sodium Sulfite 10 g Potassium Alum g Water added to make the total volume to 1000 cc.

EXAMPLE 1 According to theZ-above descriptions, two types of multi-layer type color photographic light-sensitive materials of the coupler-in-developer type color photographic system were prepared. One of them was used as a control sample and in another sample, Compound 1 1 shown hereinbefore, was added to the three silver halide emulsion layers (first layer, second layer and fourth layer) inthe amount of 40 mg per l mol of silver halide. I

Each of the multi-layer type color photographic light-sensitive materials thus prepared was subjected to the following two types of sensitometrie exposures, i.e., exposed to red light andto white light (red light green light blue light). In the above exposures, the

amount of exposure of red light was the same in both cases and the amount of exposure of the green and blue above-described components in the white light was adjusted so that they formed thesame photographic effect as the red exposure.

The samples thus exposed were developed using the developing procedures. After development,.the density of the cyan dye in the samples was obtained as a function of the amount of exposure of the red light. From the ratio of the gamma'valves of the characteristic'curves of the cyan dye images in the case of exposure to red light alone and in the case of exposure'to white light ('y /y where 7,. is the gamma value of the cyan dye image when exposed to red light and 7 is the gamma value when exposed to white light), the interimage effect was evaluated. Also, the interimage effect could be evaluated using the difference in the sensitivity obtained at a density D=0.6, that is to say, A logE [AlogE= (log E at D=0.6 of the cyan dye image when exposed to white light) (log E at D=0.6 of the cyan dye image when exposed to red light)]. In other. words, as the int'erimage effect to the cyan dye image is larger, the ratio y /y becomes larger and also ,A log E becomes larger. The results obtained are shown in Table 1.

TABLE 1 Amount 'lmg. mol of silver halide Compound (each of the three layers)] y l-y A Log E Control 0 1.25 0.2! Compound ll 40 L65 0.48

As can be seen from the above table, it is clear that with the'incorporation of Compound ll, the ratio 'y /y and A log E were increased and hence the interimage effect was increased.

EXAMPLE 2 layers) of the light-sensitive materials.

The multi-layer type color photographic light-sensitive materialsthus obtained were subjected to exposure and development as in Example I and also the density was measured as in Example 1, whereby the ratio y l-y was obtained. 0n the other hand, in order to determine the influence of the compounds shown in Table 2 on the sensitivity of the blue-sensitive layer, the multilayer type colorphotographic light-sensitive material 'wassensitometrically exposed to blue light. Thereafter each of the light-sensitive materials was processed in accordance with the developing procedures of the coupler-in-developer type color photographic system and the density of the yellow dye image was measured. From the change in the sensitivity value S (expressed as a relative value with the control sample being assumed to be obtained at D=0.6, the extent of the sensitivity of the blue layer reduced by adding the compound thereto was determined. That is to say, a lower 13 sensitivity value shows the incorporated compound reduced the sensitivity of the blue-sensitive emulsion layer to a greater extent. The y l'y values and sensitivity values S thus obtained are shown in Table 2, in which the results obtained in using the following compounds for comparison are shown.

Compound X (for comparison) Compound Y (for comparison) Cal-I Compound Z (for comparison) S O C2H5 In Table 2, the developing procedures were c65 ducted separately in Experiment Nos. l-3. In order TABLE 2 v S (Relative Amount sensitivity (mg/H101 of silver halide of blue- Coinof blue-sensitive layer) /7 sensitive pound layer Experimental Group 1 Control 0 1.15 100 1. 6 1.20 102 60 1.45 100 200 1.68 97 f 600 1.80 99 2. 100 1.28 95 200 1.35 90 3. 100 1.32 91 200 1.50 72 4. 100 1.31 95 200 1.59 85 5. 100 1.30 90 200 1.45 75 Experiment Group 2 Control 0 1.18 100 6. 100 1.35 98 200 1.62 100 7. 100 1.28 105 200 1.39 108 8. 100 1.20 101 200 1.32 96 9. 100 1.25 80 From Table 2 it can be seen that byincorporating compounds 1 to 14 of the present invention, the value of y /y could be increased without reducing the sensitivity S and hence the interimage effect was increased. I

When compound X was used, the value of 7 /7 was increased similarly but the sensitivity was greatly reduced. Also, when the merocyanine dyes Y and Z were used,'the values of 7 were essentially the same as that of the control experiment and hence compounds Y and Z do not show the effect of increasing the interimage effect as in this invention. As described above, compounds 1 to 14 in this invention have the advantages that the interimage effect was increased without greatly reducing the sensitivity.

EXAMPLE 3 According to the above-described procedures, 16

types of multilayer color photographic light-sensitive materials of the coupler-in-emulsion layer type color photographic system were prepared. One of the samples was used as a control sample and the other samples were prepared by incorporating compound 1 or compound 7 in the protective layer (the eighth layer), the blue-sensitive silver halide emulsion layer (the seventh layer), the yellow filter layer (the sixth layer), or the intermediate layer (the fourth layer) in the amount shown in Table 3 below.

The multi-layer type color photographic light-sensitive materials thus obtained were sensitometrically exposed to the following four different kinds of light, respectively. That is to say, each of the light-sensitive materials were exposed tored light, green light, blue 50 light, or white light (red light green light blue light) separately. The amount of exposure of the red component, the green component or the blue component of the white light was the same as that of the exposure to red light, the exposure to green light, or the exposure to blue light alone and the amount of exposure to each of the red light, green light and blue light was so ad jisted that the same photographic effect was obtained.

The samples thus exposed were developed using the developing process of the coupler-in-emulsion type color photographic system as described hereinbefore. After development, the ratio of the gamma values 7 W of the characteristic. curves of the cyan dye images when exposed to red light and when exposed to white light, the gamma value ratio y /7 of the characteristic curves of the magenta dye images when exposed to green light and when exposed to white light, and the gamma value ratio of 7 of the characteristic curves 1 or Compound 7 the ratios 'y l'y 7 /7 and 'y l-y were greatly increased, that is to say, the interimage effects were increased.

TABLE 3 Layer Containing Compound Com- Amount 'y /y 'y l-y YB/fly pound Conl/ 1.25 1.18 1.05

trol

l 6 1.28 1.21 1.05 Eighth Layer: 60 1.41 1.29 1.08 Protective Layer 200 1.50 1.30 1.11 600 1.65 1.31 1.15 7 100 1.40 1.25 1.12 Seventh Layer: 1 100 2/ 1.38 1.33 1.12 Blue-sensitive Layer 200. 1.57 1.35. 1.1 7 100 1.31 1.25 1.0 200 1.48 1.29 1.1 Sixth Layer: 1 100 ll 1.35 1.24 1.07 Yellow-Filter Layer 200 1.51 1.27 1.13 7 100 1.32 1.21 1.07 200 1.43 1.27 1.09 Fourth Layer: 1 100 1.39 1.22 1.07 lntermediate Layer 200 1.49 1.25 1.08

1] mg/ 100 g gelatin. 2/ mg/mol AgX With other merocyanine dyes of the general formula [1] than those described in Examples 1, 2 and 3 mentioned above, essentially similar results were obtained. Also, with other development processes than those described in the Examples, essentially the same results were obtained.

What is claimed is:

1. A multi-layer type color photographic light-sensitive material characterized in that a merocyanine dye having the following general formula [I] wherein X is a member selected from the group consisting of a sulfur atom, a selenium atom, an oxygen atom, and a group; wherein each of R,, R, and R is a member elected from the group consisting of a hydrogen atom, an alkyl group, a substituted alkyl group, whose substituents are selected from the group consisting of an alkoxy group, a hydroxy group, a vinyl group, an aryl group, a carboxy group, and a sulfo group, an aryl group, and a substituted arylgroup, whose substituents are selected from the group consisting of a carboxy group and a sulfogroup; and wherein Z represents an an atomic group necessary to complete a heterocyclic ring selected from -the group consisting of thiazolines, thiazoles, benzthiazoles, naphthothiazoles, oxazoles, benzoxazoles, naphthoxazoles, selenazoles, benzselenazoles naphthoselenazoles, benzimidazoles, naphthoimidazoles, 2-quino1ines, Z-pyridines, and indolenines, is incorporated in at least'one layer of said multi-layer type color photographic light-sensitive material, said multi-layer type color photographic lightsensitive material comprising, in order,

1. a support,

2. a subbing layer,

3. a red sensitive silver halide emulsion layer,

4. a green sensitive silver halide emulsion layer,

5.-a' blue sensitive silver halide emulsion layer,

the silver halide in at least one of the aforementioned silver halide emulsion layers containing a silver iodide content of from 1 to 10.0 mole percent, and

The silver halide in at least one of the silver halide emulsion layers being a member selected from the group consisting of Agcll, AglBr and AgCllBr, whose concentration ranges from 1 to 10.0 mole percent, the remaining silver halide emulsion layers containing a silver halide selected from the group consisting of AgBr, Agl, AgCl, AgClBr, Ag-

Cll, AglBr and AgCllBL.

2. The multi-layer type color photographic light-sensitive material as claimed in claim 1 wherein each of R,, R and R is selected from a group consisting of a hydrogen atom, a methyl group, an ethyl group, an npropyl group, an n-butyl group, an iso-butyl group, an n-amyl group, a 2-methoxyethyl group, a Z-hydroxyethyl group, an allyl group, a benzyl group, a phenyl group, a carboxymethyl group, a carboxyethyl group, a sulfomethyl group, a sulfopropyl group, a sulfobutyl group, a 4-carboxyphenethyl group, a 4-sulfophenethyl group, a phenyl group, a 4-carboxyphenyl group, and a 4-sulfophenyl group.

3. The multi-layer type color photographic light-sensitive material as claimed in claim 1 wherein the heterocyclic ring completed by Z is selected from the group consisting of the thiazolines, thiazoles, benzthiazoles, naphthothiazoles, oxazoles, benzoxazoles, naphthoxazoles, selenazoles, benzselenazoles, naphthoselenazoles, indolenines, benzimidazoles, naphthoimidazoles, Z-quinolines and Z-pyridines.

4. The multi-layer type color photographic light-sensitive -material as claimed in claim 1, wherein said merocyanine dye is incorporated in at least one of the layers consisting of the silver halide emulsion layers and the layers adjacent to the silver halide emulsion layers.

5. The multi-layer type color photographic light-sensitive material as claimed in claim 1, wherein, after development, cyan, magenta, and yellow images are formed in the red-sensitive, the green-sensitive, and the blue-sensitive silver halide emulsion layers, respectively.

6. The multi-layer type color photographic light-sew sitive material as claimed in claim I, wherein the silver halide is selected from the group consisting of silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, and silver chloro-iodobromide.

7. The multi-layer type color photographic light-sensitive material as claimed in claim 1, wherein said merocyanine dye has the formula cyanine dye has the formula 1H5 I ll l I 8. The multi-layercolor photographic light-sensitive I CZHS material as claimed in claim 1, wherein said mero- 1 cyanine dye has the formula 10 l V o 10. The multi-layer color photographic light-sensitive material as claimed in claim 1, wherein said mero- C=C cyanine dye has the formula e .N N H s v $11 H c 1 11 =(I J C=$ 0N N g I l l (1:1 5 9. The multi-layer color photographic light-sensitive material as claimed in claim 1, wherein said mero- 

1. a support,
 1. A multi-layer type color photographic light-sensitive material characterized in that a merocyanine dye having the following general formula (I) wherein X is a member selected from the group consisting of a sulfur atom, a selenium atom, an oxygen atom, and a group; wherein each of R1, R2 and R3 is a member elected from the group consisting of a hydrogen atom, an alkyl group, a substituted alkyl group, whose substituents are selected from the group consisting of an alkoxy group, a hydroxy group, a vinyl group, an aryl group, a carboxy group, and a sulfo group, an aryl group, and a substituted aryl group, whose substituents are selected from the group consisting of a carboxy group and a sulfo group; and wherein Z represents an an atomic group necessary to complete a heterocyclic ring selected from the group consisting of thiazolines, thiazoles, benzthiazoles, naphthothiazoles, oxazoles, benzoxazoles, naphthoxazoles, selenazoles, benzselenazoles naphthoselenazoles, benzimidazoles, naphthoimidazoles, 2-quinolines, 2-pyridines, and indolenines, is incorporated in at least one layer of said multi-layer type color photographic light-sensitive material, said multi-layer type color photographic light-sensitive material comprising, in order,
 2. a subbing layer,
 2. The multi-layer type color photographic light-sensitive material as claimed in claim 1 wherein each of R1, R2 and R3 is selected from a group consisting of a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an iso-butyl group, an n-amyl group, a 2-methoxyethyl group, a 2-hydroxyethyl group, an allyl group, a benzyl group, a phenyl group, a carboxymethyl group, a carboxyethyl group, a sulfomethyl group, a sulfopropyl group, a sulfobutyl group, a 4-carboxyphenethyl group, a 4-sulfophenethyl group, a phenyl group, a 4-carboxyphenyl group, and a 4-sulfophenyl group.
 3. a red sensitive silver halide emulsion layer,
 3. The multi-layer type color photographic light-sensitive material as claimed in claim 1 wherein the heterocyclic ring completed by Z is selected from the group consisting of the thiazolines, thiazoles, benzthiazoles, naphthothiazoles, oxazoles, benzoxazoles, naphthoxazoles, selenazoles, benzselenazoles, naphthoselenazoles, indolenines, benzimidazoles, naphthoimidazoles, 2-quinolines and 2-pyridines.
 4. a green sensitive silver halide emulsion layer,
 4. The multi-layer type color photographic light-sensitive material as claimed in claim 1, wherein said merocyanine dye is incorporated in at least one of the layers consisting of the silver halide emulsion layers and the layers adjacent to the silver halide emulsion layers.
 5. The multi-layer type color photographic light-sensitive material as claimed in claim 1, wherein, after development, cyan, magenta, and yellow images are formed in the red-sensitive, the green-sensitive, and the blue-sensitive silver halide emulsion layers, respectively.
 5. a blue sensitive silver halide emulsion layer, the silver halide in at least one of the aforementioned silver halide emulsion layers containing a silver iodide content of from 1 to 10.0 mole percent, and The silver halide in at least one of the silver halide emulsion layers being a member selected from the group consisting of AgclI, AgIBr and AgClIBr, whose concentration ranges from 1 to 10.0 mole percent, the remaining silver halide emulsion layers containing a silver halide selected from the group consisting of AgBr, AgI, AgCI, AgClBr, AgClI, AgIBr and AgClIBr.
 6. The multi-layer type color photographic light-sensitive material as claimed in claim 1, wherein the silver halide is selected from the group consisting of silver bromide, silver iodide, silver chloride, silver chlorobromide, silver iodobromide, and silver chloro-iodobromide.
 7. The multi-layer type color photographic light-sensitive material as claimed in claim 1, wherein said merocyanine dye has the formula
 8. The multi-layer color photographic light-sensitive material as claimed in claim 1, wherein said merOcyanine dye has the formula
 9. The multi-layer color photographic light-sensitive material as claimed in claim 1, wherein said merocyanine dye has the formula 